Organic Compounds having Taste-Modifying Properties

ABSTRACT

This disclosure relates to flavour modification and to compounds of formula (I) 
     
       
         
         
             
             
         
       
         
         
           
             wherein 
             R 1  is selected from C 6 -C 20  alkyl, and C 9 -C 25  alkenyl, 
             R 5  is C 1 -C 3  alkyl, and
           a) n is 1; and
               i) R 3  and R 4  are hydrogen and R 2  is the residue of a proteinogenic amino acid;   ii) R 2  and R 3  are methyl and R 4  is hydrogen; or R 4  is hydrogen and R 2  and R 3  form together with the carbon atom to which they are attached cyclopropyl;   iii) R 2  is hydrogen, and R 3  and R 4  together are —CH 2 —CH 2 —CH 2 —;   
               b) n is 2 or 3 and R 2 , R 3  and R 4  are hydrogen, useful in modifying flavours.

This disclosure relates to flavour modification and to compounds usefulin modifying flavours.

The addition of flavours to comestible products, that is, products takenorally either for ingestion (such as foodstuffs, confectionery andbeverages) or for spitting out (such as toothpastes and mouthwashes) isa long-established practice. The taste of flavours may be modified bythe addition of other flavor ingredients, this generally falling withinthe skill of the flavourist.

More recently, there has been a desire to modify flavours by theaddition of materials that are not in themselves standard flavoringredients, that is, they do not possess a desirable taste, if any, tobe suitable as flavor ingredient, but modify the flavour in somedesirable way when used in very low concentrations. Some examples ofthese include;

-   -   Flavour boosters. These boost a flavour or some aspect of a        flavour. For example, a sweetness booster may be added to a        comestible product to provide the same level of sweetness with a        reduced sugar content. Salt boosting is another category of such        boosting. This has become very important in the production of        health and dietary foods, where reduced levels of salt and/or        sugar are desirable.    -   Off-taste maskers. It is well known that certain desirable        flavour ingredients have the disadvantage of also providing an        undesirable off-taste. One example is the “metallic” off-taste        sometimes associated with some high-intensity sweeteners.        Maskers can block these off-tastes and allow the full desired        flavour effect to be realised without the disadvantages.    -   Mouthfeel boosters. Although not strictly a flavour        characteristic, mouthfeel can add—or detract—considerably from a        comestible composition. An undesirable mouthfeel can be        seriously disadvantageous to an otherwise desirably-flavoured        composition.

It is an additional desire of the industry to create flavours thatcapture natural, authentic flavour more fully in mass-manufacturedcomestible compositions, especially foodstuffs and beverages. Forexample, it is often desirable to make an orange-flavoured drink tasteas close as possible to fresh-squeezed orange juice. It is generallyknown that, in the preparation of commercial orange-flavoured drinks,much of the authentic orange flavour is unavoidably lost. This is trueof a wide variety of mass-manufactured foodstuffs and beverages.

It has now been found that the addition of certain compounds toflavour-containing comestible compositions can desirably modify theflavours therein in one or more of the abovementioned ways, resulting incompositions with more consumer appeal. There is therefore provided amethod of modifying the taste of a comestible composition comprising atleast one flavor co-ingredient, comprising the incorporation therein ofa flavour-modifying proportion of a compound of formula (I)

wherein

R¹ is selected from C₆-C₂₀ alky, and C₉-C₂₅ alkenyl,

R⁵ is C₁-C₃ alkyl, for example, ethyl, propyl or isopropyl, and

-   -   a) n is 1; and        -   i) R³ and R⁴ are hydrogen and R² is the residue of a            proteinogenic amino acid;        -   ii) R² and R³ are methyl and R⁴ is hydrogen; or R⁴ is            hydrogen and R² and R³ form together with the carbon atom to            which they are attached cyclopropyl;        -   iii) R² is hydrogen, and R³ and R⁴ together are            —CH₂—CH₂—CH₂—;    -   b) n is 2 or 3 and R², R³ and R⁴ are hydrogen.

The proteinogenic amino acids, having the generic structure of formula(II)

are selected from alanine (Ala; R²=methyl), cysteine (Cys; R²=CH₂—SH),aspartic acid (Asp; R²=CH₂—C(O)O⁻), phenylalanine (Phe; R²=CH₂-phenyl),glutamic acid (Glu; R²=CH₂-CH₂—C(O)O⁻), histidine (His;R²=CH₂-imidazol), isoleucine (Ile; R²=but-2-yl), lysine (Lys;R²=(CH₂)₄NH₃ ⁺), leucine (Leu; R²=isobutyl), methionine (Met;R²=(CH₂)₂—S—CH₃), asparagines (Asn; R²=CH₂C(O)NH₂), glutamine (Gln;R²=(CH₂)₂C(O)NH₂), arginine (Arg; R²=(CH₂)₃NHC(NH₂)⁺NH₂), serine (Ser;R²=CH₂OH), threonine (Thr; R²=CH(OH)CH₃), valine (Val; R²=isopropyl),tryptophan (Trp; R²=CH2-1H-indole), tyrosine(Tyr; R²=CH₂-phenol), andglycine (Gly; R²=H).

As used in relation to compounds of formula (I), unless otherwiseindicated, “alkyl” refers to linear and branched C₆-C₂₀ alkyl,preferably to C₁₂-C₂₀, for example C₁₆, C₁₈ alkyl;

“alkenyl” refers to linear and branched C₉-C₂₅ alkenyl, including C₁₀,C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, and C₂₄alkenyl, comprising 1-6 (e.g. 2,3,4, or 5 double bonds).

In one embodiment R¹ together with the carbonyl group to which it isattached is a residue of a carboxylic acid comprising 8-22 carbon atoms.

In another embodiment R¹ together with the carbonyl group to which it isattaches is a residue of a fatty acid (R¹COOH), for example, R¹ is theresidue of a C₈-C₂₂ fatty acid. The fatty acid may be mammalian ornon-mammalian. A mammalian fatty acid is a natural or synthetic fattyacid that is identical in structure to one naturally produced in amammal, including, but not limited to, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, eicosatrienoicacid, arachidonic acid, eicosapentenoic acid, and docosatetraenoic acid.A non-mammalian fatty acid is a natural or synthetic fatty acid notnormally produced by a mammal, including, but not limited to,pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoicacid, 9-trans-tetradecenoic acid, 10-trans-pentadecenoic acid,9-trans-hexadecenoic acid, 10-trans-heptadecenoic acid,10-trans-heptadecenoic acid, 7-trans-nonadecenoic acid,10,13-nonadecadienoic acid, 11-trans-eicosenoic acid, and12-transhenicosenoic acid.

The fatty acid residues may be saturated or unsaturated. If they areunsaturated, it is preferred that they have 1, 2 or 3 double bonds,which may in cis- or trans-configuration.

Non-limiting examples are compounds of formula (I) wherein R⁵ is methyl.

Further non-limiting examples are compounds of formula (I) wherein R¹ isthe residue of a fatty acid, e.g. a fatty acid residue selected fromC₁₆-C₁₈ fatty acid, which may be saturated or unsaturated.

Further non-limiting examples are compounds of formula (I) wherein R³ ishydrogen.

Further non-limiting examples are compound of formula (I) wherein R³ ishydrogen, R² the residue of a proteinogenic alpha-amino, and R¹ is theresidue of an unsaturated fatty acid comprising 2, 3 or 4 double bond.

Further non-limiting examples are compounds of formula (I) wherein R¹ isthe residue of an unsaturated fatty acid selected from myristic acid,palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,eicosatrienoic acid, arachidonic acid, eicosapentenoic acid, anddocosatetraenoic acid, geranic acid (3,7-dimethyl-2,6-octadienoic acid).

Further non-limiting examples are compounds of formula (I) selected from(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate;(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1 H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate, andmethyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.

The compounds of formula (I) can be prepared according to methods knownin the art, using commercially available starting materials, reagentsand solvents. The compounds of formula (I) may be prepared, for example,by reacting the corresponding amino acid alkyl ester with thecorresponding fatty acid. The fatty acid can either be used as the freefatty acid in combination with a coupling (dehydration) reagent or as anactivated fatty acid, for example, the fatty acid chloride.

The compounds of formula (I), as hereinabove described, impartremarkable organoleptic properties to comestible products, especiallysweet comestible products, to which they are added. In particular, theyimpart highly intense, authentic and harmonious flavour, and a roundnessand fullness to comestible products containing them.

This finding was all the more surprising considering that when applicanttasted the compounds in dilute aqueous solution, they exhibited adisappointing, faintly fatty taste profile. As such, they appeared to bequite unsuitable for use in flavour applications. Only their combinationwith flavour co-ingredients and the judicious selection of their usagelevels was it possible to discover the remarkable organolepticproperties of these compounds. Their effect on comestible products isquite unusual in that they actually complement, lift or accentuate theessential or authentic flavour and mouth feel characteristics of thefoods or beverages in which they are incorporated. Accordingly, thecompounds of the present invention find utility in a broad spectrum ofcomestible products in the food and beverage industry, as well as inhealth and wellness.

Accordingly, there is provided in another of its aspects, a method ofconferring flavour and/or mouthfeel to, or improving taste and/ormouthfeel of a comestible composition, which method comprises adding tosaid composition a compound of formula (I) defined herein.

The remarkable organoleptic effects are observed when the compounds offormula (I) are incorporated into a comestible composition containingone or more flavour co-ingredients.

Accordingly, there is provided in a further embodiment a comestiblecomposition, comprising an edible composition base, at least one flavourco-ingredient and a flavour-modifying proportion of a compound accordingto formula (I), as defined herein.

By “flavour co-ingredient” is meant an ingredient that is able tocontribute or impart or modify in a positive or pleasant way to thetaste of a comestible composition, for example, sugars, fats, salt (e.g.sodium chloride), MSG (monosodium glutamate), calcium ions, phosphateions, organic acids, proteins, purines, flavours, and mixtures thereof.Flavour co-ingredients can also include salt tastants, umami tastants,and savoury flavour compounds.

By “taste” is meant those sensations that are perceived through the oralcavity, including, salty, sweet, sour, bitter, and umami.

Non limiting examples of flavor co-ingredients include: NaCl, KCI, MSG,guanosine monophosphate (GMP), inosin monophospahte (IMP),ribonucleotides such as disodium inosinate, disodium guanylate,N-(2-hydroxyethyl)-lactamide, N-lactoyl -GMP, N-lactoyl tyramine, gammaamino butyric acid, allyl cysteine,1-(2-hydroxy-4-methoxylphenyl)-3-(pyridine-2-yl)propan-1-one, arginine,potassium chloride, ammonium chloride, succinic acid,N-(2-methoxy-4-methyl benzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(heptan-4-yl)benzo(D)(1,3)dioxole-5-carboxamide,N-(2,4-dimethoxybenzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(2-methoxy-4-methyl benzyl)-N′-2(2-(5-methyl pyridin-2-yl)ethyl)oxalamide, cyclopropyl-E,Z-2,6-nonadienamide.

In a particular embodiment, sugars are present in amounts of 0.001% to90%, more particularly 0.001% to 50%, still more particularly 0.001% to20% based on the total weight of the comestible composition.

For example sugars (e.g. sweetener such as Sucrose, High Fructose CornSyrup, Fructose and Glucose; high intensity, non-nutritive sweetenerssuch as Aspartame Acesulfame K, Sucralose, Cyclamate, Na+ Saccharin,Neotame, Rebaudioside A and/or other stevia based sweeteners) may bepresent in beverages up to 20% based on the total weight of thecomestible composition.

Examples of sweetener concentration conventionally present in beveragesare: Carbonated Soft drink : <1% to 15% sweetener; Still beverages(non-alcoholic): <1% to 15% sweetener; Juice beverages; <1% to 15%sweetener; Powdered Soft drinks: <1% to 20% sweetener; Liquidconcentrates: <1% to 20% sweetener; Alcoholic beverages: <1% to 40%sweetener; Functional beverages: <1% to 20% sweetener; Coffee basedbeverages: <1% to 15% sweetener; and Tea based beverages: <1% to 15%sweetener.

In a particular embodiment, fats are present in amounts of 0.001% to100%, more particularly 0.001% to 80%, more particularly 0.001% to 30%,still more particularly 0.001% to 5% based on the total weight of thecomestible composition.

In a particular embodiment, salt (e.g. sodium chloride) is present inamounts of 0.001% to 20%, more particularly 0.001% to 5% based on thetotal weight of the comestible composition.

In a particular embodiment, MSG is present in amounts of 0.001% to 2%based on the total weight of a comestible composition.

In a particular embodiment, calcium is present in amounts of 0.001% to50% more particularly 0.001% to 20%, still more particularly 0.001% to1% based on the total weight of the comestible composition.

In a particular embodiment, organic acids are present in amounts of0.001% to 10%, more particularly 0.001% to 7% based on the total weightof the comestible composition. Types of organic acids include citric,malic, tartaric, fumaric, lactic, acetic and succinic. Types ofcomestible products containing organic acids include beverages, such ascarbonated soft drink beverages, still beverages, Juices, powdered softdrinks, liquid concentrates, alcoholic beverages and functionalbeverages.

In a particular embodiment, phosphorus is present in an amount up to0.5% by weight of the comestible composition. Typically phosphorus willbe present as a phosphate or as phosphoric acid.

In a particular embodiment, purines are present in an amount up to 0.5%by weight of a comestible composition. The term “purines” includeribonucleotides such as IMP and GMP.

In a particular embodiment, flavours are present in an amount up to 15%by weight, for example in an amount from 0.01-15% by weight (e.g. 10-15%by weight in a snack foods, 0.1-0.5% by weight in a savoury foodproduct, 0.01-0.1% by weight in sweet products and dairy product), ofthe comestible composition.

All manner of flavours may be employed in a composition according to thepresent invention, including, but not limited to natural flavours,artificial flavours, spices, seasonings, and the like. Flavours includesynthetic flavour oils and flavouring aromatics and/or oils, oleoresins,essences, distillates, and extracts derived from plants, leaves,flowers, fruits, and so forth, and combinations comprising at least oneof the foregoing.

Flavour oils include spearmint oil, cinnamon oil, oil of wintergreen(methyl salicylate), peppermint oil, Japanese mint oil, clove oil, bayoil, anise oil, eucalyptus oil, thyme oil, cedar leaf oil, oil ofnutmeg, allspice, oil of sage, mace, oil of bitter almonds, and cassiaoil; useful flavouring agents include artificial, natural and syntheticfruit flavours such as vanilla, and citrus oils including lemon, orange,lime, grapefruit, yazu, sudachi, and fruit essences including apple,pear, peach, grape, blueberry, strawberry, raspberry, cherry, plum,prune, raisin, cola, guarana, neroli, pineapple, apricot, banana, melon,apricot, ume, cherry, raspberry, blackberry, tropical fruit, mango,mangosteen, pomegranate, papaya and the like.

Additional exemplary flavours imparted by a flavour composition includea milk flavour, a butter flavour, a cheese flavour, a cream flavour, anda yogurt flavour; a vanilla flavour; tea or coffee flavours, such as agreen tea flavour, an oolong tea flavour, a tea flavour, a cocoaflavour, a chocolate flavour, and a coffee flavour; mint flavours, suchas a peppermint flavour, a spearmint flavour, and a Japanese mintflavour; spicy flavours, such as an asafetida flavour, an ajowanflavour, an anise flavour, an angelica flavour, a fennel flavour, anallspice flavour, a cinnamon flavour, a chamomile flavour, a mustardflavour, a cardamom flavour, a caraway flavour, a cumin flavour, a cloveflavour, a pepper flavour, a coriander flavour, a sassafras flavour, asavoury flavour, a Zanthoxyli Fructus flavour, a perilla flavour, ajuniper berry flavour, a ginger flavour, a star anise flavour, ahorseradish flavour, a thyme flavour, a tarragon flavour, a dillflavour, a capsicum flavour, a nutmeg flavour, a basil flavour, amarjoram flavour, a rosemary flavour, a bayleaf flavour, and a wasabi(Japanese horseradish) flavour; a nut flavour such as an almond flavour,a hazelnut flavour, a macadamia nut flavour, a peanut flavour, a pecanflavour, a pistachio flavour, and a walnut flavour; alcoholic flavours,such as a wine flavour, a whisky flavour, a brandy flavour, a rumflavour, a gin flavour, and a liqueur flavour; floral flavours; andvegetable flavours, such as an onion flavour, a garlic flavour, acabbage flavour, a carrot flavour, a celery flavour, mushroom flavour,and a tomato flavour.

In some embodiments, said flavour composition include aldehydes andesters such as cinnamyl acetate, cinnamaldehyde, citral diethylacetal,dihydrocarvyl acetate, eugenyl 49 formate, p-methylamisol, and so forthcan be used. Further examples of aldehyde flavourings includeacetaldehyde (apple), benzaldehyde (cherry, almond), anisic aldehyde(licorice, anise), cinnamic aldehyde (cinnamon), citral, i.e.,alpha-citral (lemon, lime), neral, i.e., beta-citral (lemon, lime),decanal (orange, lemon), ethyl vanillin (vanilla, cream), heliotrope,i.e., piperonal (vanilla, cream), vanillin (vanilla, cream), alpha-amylcinnamaldehyde (spicy fruity flavours), butyraldehyde (butter, cheese),valeraldehyde (butter, cheese), citronellal (modifies, many types),decanal (citrus fruits), aldehyde C-8 (citrus fruits), aldehyde C-9(citrus fruits), aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde(berry fruits), hexenal, i.e., trans-2 (berry fruits), tolyl aldehyde(cherry, almond), veratraldehyde (vanilla), 2,6-dimethyl-5-heptenal,i.e., melonal (melon), 2,6-dimethyloctanal (green fruit), and2-dodecenal (citrus, mandarin), and the like.

Further examples of other flavours can be found in “Chemicals Used inFood Processing”, publication 1274, pages 63-258, by the NationalAcademy of Sciences.

In preparing the comestible composition, the compounds of formula (I)may be employed in any physical form. They may be used in neat form, inthe form of a stock solution; they may be used in the form of anemulsion; or they may be used in a powder form. If the compounds offormula (I) are presented in the form of a powder, the powder form canbe produced by a dispersive evaporation process, such as a spray dryingprocess. The liquid formulation may comprise a solution, suspension oremulsion comprising the compound of formula (I). The liquid formulationmay contain other ingredients such as a carrier material and/or anadjuvant suitable for flavour compositions.

In a further embodiment the compounds of formula (I) may be admixed witha flavour co-ingredient, in particular with flavours before incorporatedinto an edible composition base.

Thus there is provided in a further aspect a flavour compositioncomprising a compound of formula (I) as herein defined and at least oneflavor co-ingredient, in particular flavours, and optionally a carriermaterial and/or an adjuvant suitable for flavour composition.

The carrier material may be employed to encapsulate or to entrap in amatrix a compound of formula (I), or composition, in particular aflavour composition, containing a compound of formula (I). The role ofthe carrier material may be merely that of a processing aid or a bulkingagent, or it might be employed to shield or protect the other componentsfrom the effects of moisture or oxygen or any other aggressive media.The carrier material might also act as a means of controlling therelease of flavour the product when consumed.

Carrier materials may include mono, di- or trisaccharides, natural ormodified starches, hydrocolloids, cellulose derivatives, polyvinylacetates, polyvinylalcohols, proteins or pectins. Example of particularcarrier materials include sucrose, glucose, lactose, levulose, fructose,maltose, ribose, dextrose, isomalt, sorbitol, mannitol, xylitol,lactitol, maltitol, pentatol, arabinose, pentose, xylose, galactose,maltodextrin, dextrin, chemically modified starch, hydrogenated starchhydrolysate, succinylated or hydrolysed starch, agar, carrageenan, gumarabic, gum accacia, tragacanth, alginates, methyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethylcellulose, derivatives and mixtures thereof. Of course, the skilledaddresse with appreciate that the cited materials are hereby given byway of example and are not to be interpreted as limiting the invention.

By “flavour adjuvant” is meant an ingredient capable of impartingadditional added benefit to compositions of the present invention suchas a colour, light resistance, chemical stability and the like. Suitableadjuvants include solvents (including water, alcohol, ethanol,triacetine, oils, fats, vegetable oil and miglyol), binders, diluents,disintegrating agents, lubricants, colouring agents, preservatives,antioxidants, emulsifiers, stabilisers, anti-caking agents, and thelike. In a particular embodiment, the flavour composition comprises ananti-oxidant. Said anti-oxidants may include vitamin C, vitamin E,rosemary extract, antrancine, butylated hydroxyanisole (BHA) andbutylated hydroxytoluene (BHT).

Examples of such carriers or adjuvants for flavour compositions may befound in for example, “Perfume and Flavour Materials of Natural Origin”,S. Arctander, Ed., Elizabeth, N.J., 1960; in “Perfume and FlavourChemicals”, S. Arctander, Ed., Vol. I & II, Allured PublishingCorporation, Carol Stream, USA, 1994; in “Flavourings”, E. Ziegler andH. Ziegler (ed.), Wiley-VCH Weinheim, 1998, and “CTFA CosmeticIngredient Handbook”, J. M. Nikitakis (ed.), 1st ed., The Cosmetic,Toiletry and Fragrance Association, Inc., Washington, 1988.

Other suitable and desirable ingredients of flavour compositions aredescribed in standard texts, such as “Handbook of Industrial ChemicalAdditives”, ed. M. and I. Ash, 2nd Ed., (Synapse 2000).

Flavour compositions according to the present invention may be providedin any suitable physical form. For example, they may be in the form ofoils, emulsions or dispersions in a hydrous liquid or organic liquidsuitable for use in comestible products, or solid form, such as powders.

If the flavour compositions are to be provided in the form of a powderedcomposition, they may be prepared by dispersive evaporation techniquesgenerally known in the art, such as spray drying.

Accordingly, in a further embodiment there is provided a method offorming a powder composition, comprising the steps of providing a liquidcomposition comprising a compound of the formula (I) and one or moreoptional ingredients selected from at least one flavour co-ingredient, acarrier material and an adjuvant, and dispersively evaporating saidliquid composition to form a powder composition.

In this manner, a compound of formula (I) or a flavour compositioncomprising said compound may be presented in a powder form.

The liquid composition used in the preparation of a powder may be in theform of a solution, emulsion, dispersion or slurry. The liquid maycontain water, and/or an organic liquid, such as ethanol, glycerol,triacetine, miglyol (MCT) that is acceptable for use in comestibleproducts.

Powder compositions may be prepared according to methods and apparatusknown in the art for producing powders on an industrial scale. Aparticularly suitable method is spray drying. Spray drying techniquesand apparatus are well known in the art and need no detailed discussionherein. The spray drying techniques, apparatus and methods described inUS2005/0031769 and US2013/0022728, as well as those techniques,apparatus and methods described in those documents are suitable forproducing powder compositions and are herein incorporated by referencein their entirety.

As stated hereinabove, compounds of formula (I) or flavour compositionscontaining such compounds can be incorporated into comestible products,and a comestible composition or a flavor composition containing such acompound of formula (I) form another aspects of the present invention.

The term “comestible composition” refers to products for consumption bya subject, typically via the oral cavity (although consumption may occurvia non-oral means such as inhalation), for at least one of the purposesof enjoyment, nourishment, or health and wellness benefits. Comestibleproducts may be present in any form including, but not limited to,liquids, solids, semi-solids, tablets, capsules, lozenges, strips,powders, gels, gums, pastes, slurries, syrups, aerosols and sprays. Theterm also refers to, for example, dietary and nutritional supplements.Comestible products include compositions that are placed within the oralcavity for a period of time before being discarded but not swallowed. Itmay be placed in the mouth before being consumed, or it may be held inthe mouth for a period of time before being discarded. A comestiblecomposition as herein above defined includes compositions whose taste ismodified in the manner described herein by the addition of compounds offormula (I).

Broadly, the comestible composition includes, but is not limited tofoodstuffs of all kinds, confectionery products, baked products, sweetproducts, savoury products, fermented products, dairy products,beverages and oral care products.

In a particular embodiment the term “comestible products” refers toproducts for consumption by a subject, typically via the oral cavity(although consumption may occur via non-oral means such as inhalation),for one of the purposes of enjoyment or nourishment.

In a more particular embodiment the term “comestible products” refers toproducts for consumption by a subject, typically via the oral cavity(although consumption may occur via non-oral means such as inhalation),for the purpose of enjoyment. Still more particularly, the term refersto foodstuffs and beverages.

Exemplary foodstuffs include, but are not limited to, chilled snacks,sweet and savoury snacks, fruit snacks, chips/crisps, extruded snacks,tortilla/corn chips, popcorn, pretzels, nuts, other sweet and savourysnacks, snack bars, granola bars, breakfast bars, energy bars, fruitbars, other snack bars, meal replacement products, slimming products,convalescence drinks, ready meals, canned ready meals, frozen readymeals, dried ready meals, chilled ready meals, dinner mixes, frozenpizza, chilled pizza, soup, canned soup, dehydrated soup, instant soup,chilled soup, uht soup, frozen soup, pasta, canned pasta, dried pasta,chilled/fresh pasta, noodles, plain noodles, instant noodles, cups/bowlinstant noodles, pouch instant noodles, chilled noodles, snack noodles,dried food, dessert mixes, sauces, dressings and condiments, herbs andspices, spreads, jams and preserves, honey, chocolate spreads, nut-basedspreads, and yeast-based spreads.

Exemplary confectionery products include, but are not limited to,chewing gum (which includes sugarized gum, sugar-free gum, functionalgum and bubble gum), centerfill confections, chocolate and otherchocolate confectionery, medicated confectionery , lozenges, tablets,pastilles, mints, standard mints, power mints, chewy candies, hardcandies, boiled candies, breath and other oral care films or strips,candy canes, lollipops, gummies, jellies, fudge, caramel, hard and softpanned goods, toffee, taffy, liquorice, gelatin candies, gum drops,jelly beans, nougats, fondants, combinations of one or more of theabove, and edible flavour compositions incorporating one or more of theabove.

Exemplary baked products include, but are not limited to, alfajores,bread, packaged/industrial bread, unpackaged/artisanal bread, pastries,cakes, packaged/industrial cakes, unpackaged/artisanal cakes, cookies,chocolate coated biscuits, sandwich biscuits, filled biscuits, savourybiscuits and crackers, bread substitutes,

Exemplary sweet products include, but are not limited to, breakfastcereals, ready-to-eat (“rte”) cereals, family breakfast cereals, flakes,muesli, other ready to eat cereals, children's breakfast cereals, hotcereals,

Exemplary savoury products include, but are not limited to, salty snacks(potato chips, crisps, nuts, tortilla-tostada, pretzels, cheese snacks,corn snacks, potato-snacks, ready-to-eat popcorn, microwaveable popcorn,pork rinds, nuts, crackers, cracker snacks, breakfast cereals, meats,aspic, cured meats (ham, bacon), luncheon/breakfast meats (hotdogs, coldcuts, sausage), tomato products, margarine, peanut butter, soup (clear,canned, cream, instant, UHT),canned vegetables, pasta sauces.

Exemplary dairy products include, but are not limited to, cheese, cheesesauces, cheese-based products, ice cream, impulse ice cream, singleportion dairy ice cream, single portion water ice cream, multi-packdairy ice cream, multi-pack water ice cream, take-home ice cream,take-home dairy ice cream, ice cream desserts, bulk ice cream, take-homewater ice cream, frozen yoghurt, artisanal ice cream, dairy products,milk, fresh/pasteurized milk, full fat fresh/pasteurized milk, semiskimmed fresh/pasteurized milk, long-life/uht milk, full fat longlife/uht milk, semi skimmed long life/uht milk, fat-free long life/uhtmilk, goat milk, condensed/evaporated milk, plain condensed/evaporatedmilk, flavoured, functional and other condensed milk, flavoured milkdrinks, dairy only flavoured milk drinks, flavoured milk drinks withfruit juice, soy milk, sour milk drinks, fermented dairy drinks, coffeewhiteners, powder milk, flavoured powder milk drinks, cream, yoghurt,plain/natural yoghurt, flavoured yoghurt, fruited yoghurt, probioticyoghurt, drinking yoghurt, regular drinking yoghurt, probiotic drinkingyoghurt, chilled and shelf-stable desserts, dairy-based desserts,soy-based desserts.

Exemplary beverages include, but are not limited to, flavoured water,soft drinks, fruit drinks, coffee-based drinks, tea-based drinks,juice-based drinks (includes fruit and vegetable), milk-based drinks,gel drinks, carbonated or non-carbonated drinks, powdered drinks,alcoholic or non-alcoholic drinks.

Exemplary fermented foods include, but are not limited to, Cheese andcheese products, meat and meat products, soy and soy products, fish andfish products, grain and grain products, fruit and fruit products.

The compounds of formula (I), when added to a flavour composition and/ora comestible composition, may modify any aspect of the temporal profileof taste and/or mouthfeel of a comestible composition.

Compounds of formula (I) or flavour compositions containing same may beadded to comestible products in widely carrying amounts. The amount willdepend on the nature of the comestible composition to be flavoured, andon the desired effect, as well as on the nature of the ingredientspresent in said composition. In order to obtain the remarkablebeneficial effects attributed to the presence of the compounds offormula (I), the flavour composition should be employed in amounts suchthat the compounds of formula (I) are present in amounts of 1 part perbillion to 10 parts per million based on the total weight of thecomestible composition. Whereas amounts higher than this can beemployed, the beneficial effects are considerably less apparent andundesirable off-notes can become increasingly apparent.

Interesting organoleptic effects, e.g. salt, alcohol or coolant boostingeffects, in comestible products containing salt or alcohol or coolantcompounds can be achieved when compounds of the formula (I) are employedat levels of 1 to 100 ppb.

Interesting organoleptic effects, for example umami boosting effects, incomestible products containing umami tastants can be achieved whencompounds of the formula (I) are employed at levels of 100 to 250 ppb.

Interesting organoleptic effects, in particular mouthfeel boostingeffects, in comestible products can be achieved when compounds of theformula (I) are employed at levels of 250 to 500 ppb.

Interesting organoleptic effects, e.g. fat boosting effects, incomestible products containing fats can be achieved when compounds ofthe formula (I) are employed at levels of 500 to 1000 ppb.

It is particularly advantageous to incorporate compounds of formula (I)into comestible products that are formed under conditions of hightemperature, such as baking, frying or which are processed by heattreatments such as pasteurization or under UHT conditions. Under highpreparation or processing temperatures, volatile flavour ingredients maybe lost or degraded with the result that flavour intensity can bereduced and the essential and authentic flavour characteristics can bediminished. Such edible products include dairy products, snack foods,baked products, powdered soft drinks and similar dry mixes, and thelike, fats and condiments, mayonnaise, dressings, soups and bouillons,and beverages.

A particularly preferred class of comestible composition according tothe present invention are powdered soft drinks and similar dry mixapplications. Dry mix applications are known in the art and includedproducts in powder form that are intended to be reconstituted beforeconsumption. They include powdered soups, powdered cake mixes, powderedchocolate drinks, instant coffees, seasonings and fonds, and the like.

Dry powders formed by dispersive evaporation processes, such as spraydrying, represent a very convenient vehicle to deliver flavour oilquality flavours to comestible products.

Another particularly preferred class of comestible composition accordingto the present invention are snack foods. Snack foods are a category ofproduct well known to the skilled person in the food industry. Theseproducts are described above and include, without limitation, pretzels,corn chips, potato chips, puffed products, extruded products, tortillachips and the like. Still more particularly, the invention is concernedwith low fat snack food compositions. Low fat snack food compositionscontain less that 30% by weight fat, more particularly between 5 to 25%by weight of fat.

A problem with reducing fat in a snack food composition is the loss intaste and texture. Fats play an important role in the way that doughbehaves during processing and greatly affect the quality, flavor andtexture of ready-to-eat products. As the fat content in snack productsis reduced or replaced with other ingredients (e.g., non-digestible fat,protein, fiber, gums), adverse organoleptic effects (e.g., mouthcoating, drying, lack of crispness and lack of flavour) are increased.The adverse organoleptic effects result in products having reducedpalatability.

Considerable efforts have been expended in devising flavour compositionsto overcome the problems associated with low fat snack food products.Flavours may be applied to a snack food as topical coatings in the formof dry powders and/or as liquids (e.g., oil-based, water-based). Anotherapproach has been to add flavour to the dough.

Despite these various approaches which have been taken to improveconsumer appeal and palatability of snack foods, and particularly lowfat snack foods, there is still a need for improved low-fat snack foodshaving coatings applied thereto with the visual appeal, flavor, andtexture of full-fat snack foods.

Compounds according to formula (I) or flavour compositions containingsame can be incorporated into snack foods to impart an impactful flavourand a mouthfeel with a remarkable roundness and fullness. Furthermore,the taste and mouthfeel effects can be achieved even in low fat snackfoods.

Accordingly, the invention provides in another of its aspects a snackfood comprising a flavour composition as hereinabove described. In aparticular embodiment of the invention the snack food has a fat contentof about 40% or less by weight based on the total weight of the snackfood, more particularly about 30% or less, still more particularly 25%or less, more particularly still about 10% or less, still moreparticularly about 5% or less, still more particularly about 3% or less.

Examples of snack foods are described above and include productsprocessed by oven baking, extrusion or frying, and which are made frompotato and/or corn and/or various grains such as rice or wheat.

Another particularly preferred class of comestible composition accordingto the present invention is alcoholic beverages.

Applicant surprisingly found that compounds according to formula (I)incorporated into an alcoholic beverage had the effect of increasing thealcohol impact of the beverage.

Accordingly, the invention provides in another of its aspects analcoholic beverage comprising a compound according to formula (I).

In yet another aspect of the invention there is provided a method ofproducing a heightened alcoholic impression in an alcoholic beverage byincorporating into said beverage a compound according to formula (I).

Compounds of formula (I) may be incorporated into said alcoholicbeverage in amounts of 1 ppb to 1 ppm.

Another class of comestible products are products taken orally in theform of tablets, capsules, powders, multiparticulates and the like. Suchcompounds may include pharmaceutical dosage forms or nutraceuticaldosage forms. Certain groups of people have problems swallowing tabletsor capsules, powders, multi-particulates and the like. This problem canbe particularly pronounced in certain consumer groups, such as childrenand the very old or infirm. Applicant surprisingly found that compoundsaccording to the formula (I) when taken into the oral cavity produce apronounced salivating effect. Incorporating the compounds into theseforms, particularly as part of a coating around said dosage forms canease the swallowing process for consumers, in particular children andthe old or infirm.

Accordingly, the invention provides in another of its aspects an orallyadministrable dosage form, in particular in the form of tabletscapsules, powders or multiparticulates comprising a compound accordingto the formula (I).

Another preferred class of comestible composition is baked goods.Compounds of the formula (I) may be incorporated topically or in-dough.Incorporated at levels of 1 ppb to 1 ppm, the compounds of formula (I)render baked products less dry and more succulent.

Other preferred class of comestible products are caloric or non-caloricbeverages containing carbohydrate sweeteners, such as sucrose, highfructose corn syrup, fructose and glucose, or high intensity,non-nutritive sweeteners such as aspartame, acesulfame K, sucralose,cyclamate, sodium saccharin, neotame, rebaudioside A, and/or otherstevia-based sweeteners; as well as other optional ingredients such asjuices, organic acids such as citric acid, alcohol and functionalingredients.

Incorporated at levels of 1 ppb to 10 ppm, compounds of formula (I)impart to said beverages containing sweeteners at levels of less than 1%and up to about 20%, an upfront sweetness and mouthfeel that isreminiscent of sugar.

Other preferred comestible products are savoury compositions, inparticular those that are soy-based or fish-based.

Incorporated at levels of 1 ppb to 10 ppm, in a soy-based composition(such as soy sauce) or a fish-based composition (such as fish sauce)containing 5 to 40% salt, the compositions are found to exhibit strongumami tastes that are long-lasting and rich.

Another preferred comestible composition is a clouded beveragecomposition.

Certain beverages such as juices have relatively higher turbidity andthus have an opaque appearance. Often, it is desired that the beveragehave a relatively high turbidity. This might be desirable to provide amore natural appearance to beverages with low juice content, or it mightbe for reasons related to masking sedimentation or “ringing” (whereflavour or colour oils rise to the surface of a container duringstorage). Clouded beverages are usually formed by means of a cloudingagent. Clouding agents are usually supplied in the form of emulsions, orthe clouding agent may be part of a powdered beverage that uponreconstitution will formed an emulsion providing a permanent cloud tothe beverage.

Compounds of the formula (I), in addition to their remarkableorganoleptic properties, can lend stability to clouding agents and tobeverage compositions containing same.

Other preferred comestible products are those compositions that areformed by a process of ripening. In food processing, it frequentlyoccurs that a food needs to remain for a prolonged period of time andunder well-defined conditions to obtain the food with the requisite andrecognised quality. A commonly used term for this process is ripening.Ripening is well known in the processing of certain types of cheese,meat, soy-sauce and wine, as well as beer sausage, sauerkraut, tempehand tofu. There are also specific steps that are carried out forspecific reasons (such as water-removal, or off-note removal) that havebeneficial effects on the food products. Examples of this are theconching of chocolate and the drying of noodles, vegetables and fruits.The transformations that improve the quality of the food are induced bychemical conversions, enzymatically catalysed conversions orfermentative transformations. All of these conversions are slow andtherefore expensive; they are also not fully predictable orcontrollable.

The compounds of formula (I), having regard to their remarkable propertyof adding to the authentic taste characteristics of the comestibleproducts in which they are incorporated, may be added to an edibleproduct during its ripening process in order to reduce storage timewithout adversely influencing the taste quality of the ripened product.

Accordingly, in another aspect of the invention there is provided amethod of ripening a product selected from the group consisting ofcheese, meat, soy-sauce and wine, beer, sausage, sauerkraut, tempeh andtofu, comprising the step of ripening the product in the presence of acompound according to the formula (I).

In another aspect of the invention there is provided a method ofconching chocolate, said method comprising the step of adding to thechocolate a compound according to the formula (I), or a flavourcomposition containing same.

The invention is now further described with reference to the followingnon-limiting examples. These examples are for the purpose ofillustration only, and it is understood that variations andmodifications can be made by one skilled in the art.

EXAMPLE 1 Methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate

In a 250 mL round-bottomed flask fitted with a stirrer, cooler anddropping funnel methyl 2-amino-4-methylpentanoate, HCl (3 g, 16.51 mmol)was dissolved in dichloromethane (DCM; 100 ml). Triethyl amine (1.519 g,15.01 mmol) was added at minus 15° C. Linoleic acid (4.21 g, 15.01 mmol)was added while stirring.

A solution of N,N-dicyclohexylcarbodiimide (DCC; 3.10 g, 15.01 mmol) in10 mL of DCM was added dropwise at 0° C. The reaction mixture wasstirred at 0° C. for 1 hour and stirring was continued at roomtemperature for 3 hours.

The formed dicyclohexyl urea was removed by filtration from the reactionmixture. Filtrate was washed with a saturated sodium bicarbonatesolution, diluted hydrochloric acid solution and water. Organic layerwas separated, dried and evaporated to yield 3 g of an oil. This oil waspurified by flash column chromatography, eluent DCM/methanol methyl4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate was obtained ina purity of 95%, yield: 31%.

¹H NMR (600 MHz, CHLOROFORM-d) ppm 0.87-0.92 (t, J=6.82 Hz, 3H, H—C(18))0.93-0.97 (m, 6H, H—C(23, 24)) 1.26-1.46 (m, 14H, H—C(4, 5, 6, 7, 15,16, 17) 1.45-1.70 (m, 5H, H—C(3, 21, 22)) 2.13 (m, 4H, H—C(8, 14))2.13-2.33 (m, 2H, H—C(2)) 2.69-2.88 (m, 2H, H—C(11)) 3.70-3.90 (s, 3H,H—C(25)) 4.62-4.74 (m, 1H, H—C(20)) 5.30-5.49 (m, 4H, H—C(9, 10, 12, 13)5.83 (d, J=7.56 Hz, 1H, H—N(26))

¹³C NMR (151 MHz, CHLOROFORM-d) ppm 14.08 (C(18)), 21.95 (C(24)), 22.77C(23)), 24.85 C(22)) 25.53 C(3)), 25.58 C(11)) 27.10-27.31 (C(8, 14)),29.02-29.69 C(4, 5, 6, 7, 15)) 31.48 C(16)), 36.54 C(2)), 41.76 C(21)),41.76 C(21)), 50.47 C(20)), 52.22 C(25)), 127.79-128.08 C(9, 10, 12,13), 172.83 C(19), 173.75 C(1))

EXAMPLE 2 (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate

According to the same procedure of Example 1, (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate was prepared fromleucine methyl ester and geranic acid in a yield of 13%.

¹H NMR (600 MHz, DMSO-d₆) δ ppm 0.67-0.93 (m, 6H) 1.37-1.74 (m, 10H)1.93-2.17 (m, 6H) 2.41-2.65 (m, 1H) 3.50-3.66 (m, 3H) 4.25 (ddd,J=10.05, 7.13, 5.15 Hz, 1H) 4.96-5.14 (m, 1H) 5.60-5.75 (m, 1H)7.95-8.15 (m, 1H)

¹³C NMR (151 MHz, DMSO-d₆) δ ppm 17.46 (s, 1C) 17.51 (s, 1C) 17.74 (s,1C) 21.22 (s, 1C) 22.73 (s, 1C) 24.27 (s, 1C) 24.29 (s, 1C) 24.56 (s,1C) 25.43 (s, 1C) 25.45 (s, 1C) 25.65 (s, 1C) 26.34 (s, 1C) 32.20 (s,1C) (s, 1C) 39.64 (s, 1C) 39.79 (s, 1C) 39.92 (s, 1C) 40.19 (s, 1C)49.89 (s, 1C) 49.95 (s, 1C) 51.67 (s, 1C) 51.69 (s, 1C) 117.91 (s, 1C)123.40 (s, 1C) 124.02 (s, 1C) 131.40 (s, 1C) 152.82 (s, 1C) 166.06 (s,1C) 173.34 (s, 1C)

EXAMPLE 3 (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate

According to the same procedure of Example 1, (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)propanoate was prepared from alaninemethyl ester and geranic acid in a yield of 13%.

¹H NMR (600 MHz, DMSO-d₆) δ ppm 1.12-1.27 (m, 6H) 1.45-1.66 (m, 12H)1.76 (d, J=1.37 Hz, 2H) 1.88-2.14 (m, 9H) 2.47 (s, 1H) 4.09-4.29 (m, 1H)4.96-5.15 (m, 1H) 5.59-5.72 (m, 1H) 8.13 (d, J=6.87 Hz, 1H)

¹³C NMR (151 MHz, DMSO-d₆) δ ppm 16.95 (s, 1C) 17.49 (s, 1C) 17.53 (s,1C) 17.72 (s, 1C) 24.60 (s, 1C) 25.46 (s, 1C) 25.65 (s, 1C) 26.38 (s,1C) 32.25 (s, 1C) 40.18 (s, 1C) 47.24 (s, 1C) 47.27 (s, 1C) 51.71 (s,1C) 51.73 (s, 1C) 117.90 (s, 1C) 118.66 (s, 1C) 123.39 (s, 1C) 124.06(s, 1C) 131.41 (s, 1C) 152.86 (s, 1C) 165.80 (s, 1C) 173.41 (s, 1C)

EXAMPLE 4 (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate

According to the same procedure of Example 1, (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate was preparedfrom proline methyl ester and geranic acid in a yield of 65%.

¹H NMR (600 MHz, DMSO-d₆) δ ppm 1.43-1.58 (m, 3H) 1.58-1.67 (m, 3H)1.69-1.97 (m, 6H) 1.97-2.19 (m, 4H) 3.12-3.38 (m, 2H) 3.38-3.52 (m, 2H)3.52-3.71 (m, 3H) 4.26 (dd, J=8.59, 4.47Hz, 1H) 4.47-4.59 (m, 1H)4.98-5.13 (m, 1H) 5.61 (s, 1H) 5.72 (d, J=0.69 Hz, 1H) 5.79-5.91 (m, 1H)

¹³C NMR (151 MHz, DMSO-d₆) δ ppm 17.51 (s, 1C) 17.59 (s, 1C) 18.02 (s,1C) 24.50 (s, 1C) 25.44 (s, 1C) 25.47 (s, 1C) 25.65 (s, 1C) 28.75 (s,1C) 46.85 (s, 1C) 51.66 (s, 1C) 58.07 (s, 1C) 117.17 (s, 1C) 123.52 (s,1C) 131.37 (s, 1C) 165.14 (s, 1C) 172.67 (s, 1C)

EXAMPLE 5 (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate

According to the same procedure of Example 1, (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate wasprepared from histidine methyl ester and geranic acid in a yield of 13%.

¹H NMR (600 MHz, DMSO-d₆) δ ppm 1.45-1.67 (m, 6H) 1.92-2.13 (m, 6H) 2.47(s, 2H) 2.82 (d, J=12.37Hz, 2H) 3.55 (s, 2H) 4.34-4.48 (m, 1H) 4.94-5.08(m, 1H) 5.53-5.71 (m, 1H) 6.50-6.89 (m, 1H) 7.49 (br. s., 1H) 7.96-8.22(m, 1H) 11.70-11.87 (m, 1H)

¹³C NMR (151 MHz, DMSO-d₆) δ ppm 18.04 (s, 1C) 18.08 (s, 1C) 18.27 (s,1C) 24.05 (s, 1C) 25.11 (s, 1C) 25.95 (s, 1C) 25.99 (s, 1C) 26.02 (s,1C) 26.05 (s, 1C) 26.17 (s, 1C) 26.89 (s, 1C) 27.18 (s, 1C) 31.22 (s,1C) 32.79 (s, 1C) 40.58 (s, 1C) 40.69 (s, 1C) 52.24 (s, 1C) 52.80 (s,1C) 118.51 (s, 1C) 123.94 (s, 1C) 124.57 (s, 1C) 131.96 (s, 1C) 135.41(s, 1C) 166.48 (s, 1C) 207.02 (s, 1C)

EXAMPLE 6 Methyl1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate (N-linoleoylproline methyl ester)

According to the same procedure of Example 1, methyl1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate was preparedfrom proline methyl ester and linoleic acid in a yield of 25%.

¹H NMR (600 MHz, CHLOROFORM-d) δ ppm 0.86-0.93 (t, J=6.87, 3H, H—C(18))1.24-1.40 (m, 14H, H—C(4, 5, 6, 7, 15, 16, 17)) 1.63-1.71 (m, 2H,H—C(3)) 1.95-2.02 (m, 2H, H—C(22) 2.02-2.12 (m, 5H, H—C(8, 14, 21)2.12-2.22 (m, 1H, H—C(21)) 2.23-2.38 (m, 2H, H—C2))) 4.49 (dd, J=8.59,3.78Hz, 1H, H—C20)) 5.22-5.49 (m, 4H, H—C(9, 10, 12, 13)

¹³C NMR (151 MHz, CHLOROFORM-d) δ ppm 14.07 (C(18)) 22.57 (C(17)) 24.57(C(3)) 24.82 (C(22)) 25.61 (C(11)) 27.15-27.27 (C(8, 14) 29.07-29.72(C(4, 5, 6, 7, 15, 21)) (C) 31.51 (C(16)) 34.47 (C(2)) 46.97 (C(23))52.15 (C(24)) 58.54 (C(20)) 127.84-128.03 (C(10, 12)) 130.03-130.25(C(9, 13)) 172.08 (C(1, 19))

EXAMPLE 7 Methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate(N-linolenoyl Alanine Methyl Ester)

According to the same procedure of Example 1, methyl2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate was prepared fromalanine methyl ester and linolenic acid in a yield of 25%.

¹H NMR (600 MHz, DMSO-d₆) δ ppm 0.92 (t, J=7.39Hz, 3H) 1.14-1.19 (m, 1H)1.17-1.39 (m, 20H) 1.39-1.59 (m, 3H) 1.92-2.13 (m, 9H) 2.62-2.84 (m, 5H)3.60 (s, 4H) 4.23 (t, J=7.22Hz, 1H) 5.22-5.40 (m, 7H) 8.20 (d, J=6.87Hz, 1H)

¹³C NMR (151 MHz, DMSO-d₆) δ ppm 14.43 (s, 1C) 14.62 (s, 1C) 17.46 (s,1C) 20.56 (s, 1C) 22.51 (s, 1C) 25.63 (s, 1C) 25.67 (s, 1C) 25.72 (s,1C) 27.13 (s, 1C) 27.17 (s, 1C) 29.08 (s, 1C) 29.11 (s, 1C) 29.21 (s,1C) 29.26 (s, 1C) 29.55 (s, 1C) 31.43 (s, 1C) 35.40 (s, 1C) 47.93 (s,1C) 52.23 (s, 1C) 127.48 (s, 1C) 128.06 (s, 1C) 128.26 (s, 1C) 128.42(s, 1C) 128.45 (s, 1C) 130.24 (s, 1C) 130.41 (s, 1C) 132.00 (s, 1C)172.63 (s, 1C) 173.79 (s, 1C)

EXAMPLE 8 Mango Flavoured Beverage

A mango-flavoured beverage was prepared using a standard mango flavour(0.05% w/w), mango juice (0.18% w/w), sugar (8% w/w) and citric acid(0.1% w/w). The drinks were evaluated by a panel of experienced tasters.

-   -   a) When 0.5 ppm of N-linoleoyl proline methyl ester (Example 6)        was dosed to the mango drink the panel agreed that this drink        tasted more fruity and peach-like than the reference drink.    -   b) When 0.5 ppm of N-linolenoyl alanine methyl ester (Example 7)        was dosed to the mango drink the panel agreed that this drink        tasted more fully, more fatty than the reference drink.

1. A flavour composition comprising a flavour co-ingredient and acompound of formula (I)

wherein R¹ is selected from C₆-C₂₀ alkyl, and C₉-C₂₅ alkenyl, R⁵ isC₁-C₃ alkyl, and a) when n is 1; i) R³ and R⁴ are hydrogen and R² is theresidue of a proteinogenic amino acid; or ii) R² and R³ are methyl andR⁴ is hydrogen; or R⁴ is hydrogen and R² and R³ form together with thecarbon atom to which they are attached cyclopropyl; or, iii) R² ishydrogen, and R³ and R⁴ together are —CH₂—CH₂—CH₂—; or, b) when n is 2or 3, R², R³ and R⁴ are hydrogen.
 2. A flavour composition according toclaim I wherein the flavour co-ingredient is selected from: sugars,fats, salts, monosodium glutamate, calcium ions, phosphate ions, organicacids, proteins, purines, flavours, and mixtures thereof.
 3. Acomestible product comprising a compound of formula (I)

wherein: R¹ is selected from C₆-C₂₀ alkyl, and C₉-C₂₅ alkenyl, R⁵ isC₁-C₃ alkyl, and a) when n is 1; i) R³ and R⁴ are hydrogen and R² is theresidue of a proteinogenic amino acid; or ii) R² and R³ are methyl andR⁴ is hydrogen; or R⁴ is hydrogen and R² and R³ form together with thecarbon atom to which they are attached cyclopropyl; or, iii) R² ishydrogen, and R³ and R⁴ together are —CH₂—CH₂—CH₂—; b) when n is 2 or 3,and R², R³ and R⁴ are hydrogen.
 4. A flavour composition according toclaim 1, wherein the compound of formula (I) is selected from:(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate;(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-24(9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and,methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.
 5. Amethod of modifying the taste of comestible composition comprising atleast one flavour co-ingredient, the method comprising the step ofadding to or including in said comestible composition a compound offormula (I)

wherein R¹ is selected from C₆-C₂₀ alkyl, and C₉-C₂₅ alkenyl, R⁵ isC₁-C₃ alkyl, and a) when n is 1; i) R³ and R⁴ are hydrogen and R² is theresidue of a proteinogenic amino acid; or, ii) R² and R³ are methyl andR⁴ is hydrogen; or R⁴ is hydrogen and R² and R³ form together with thecarbon atom to which they are attached cyclopropyl; or, iii) R² ishydrogen, and R³ and R⁴ together are —CH₂—CH₂—CH₂—; b) when n is 2 or 3,R², R³ and R⁴ are hydrogen.
 6. A taste-modifying agent adapted for usein a consumable product, the said taste-modifying agent comprising acompound of formula (I)

wherein R¹ is selected from C₆-C₂₀ alkyl, and C₉-C₂₅ alkenyl, R⁵ isC₁-C₃ alkyl, and a) when n is 1; i) R³ and R⁴ are hydrogen and R² is theresidue of a proteinogenic amino acid; or, ii) R² and R³ are methyl andR⁴ is hydrogen; or R⁴ is hydrogen and R² and R³ form together with thecarbon atom to which they are attached cyclopropyl; or, iii) R² ishydrogen, and R³ and R⁴ together are —CH₂—CH₂—CH₂—; b) when n is 2 or3R², R³ and R⁴ are hydrogen.
 7. A flavour composition according to claim1, wherein the compound of formula (I) is selected from: (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and,methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.
 8. Acomestible product according to claim 3, wherein the compound of formula(I) is selected from: (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and,methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.
 9. Themethod according to claim 5, wherein the compound of formula (I) isselected from: (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-2-(9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and,methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.
 10. Thetaste-modifying agent according to claim 6, wherein the compound offormula (I) is selected from: (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate;methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate;methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and,methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate.